CN106170516B - Oligomeric organosilanes, method for the production thereof and use thereof in rubber mixtures - Google Patents

Oligomeric organosilanes, method for the production thereof and use thereof in rubber mixtures Download PDF

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CN106170516B
CN106170516B CN201580004673.7A CN201580004673A CN106170516B CN 106170516 B CN106170516 B CN 106170516B CN 201580004673 A CN201580004673 A CN 201580004673A CN 106170516 B CN106170516 B CN 106170516B
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radical
structural units
oligomeric organosilane
oligomeric
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CN106170516A (en
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A·布卢默
R·默泽
S·罗森斯廷格尔
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Evonik Operations GmbH
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences

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Abstract

The invention relates to oligomeric organosilanes containing at least two different structural units in the molecule, selected from structural units A, B, C and D, connected in any desired linear, branched or cyclic arrangement, wherein at least one R, R 1, R 2, R 3, R 4 or R 7 group is an alkylpolyether group-O- (R 5 -O) m -R 6, to a process for their preparation and to their use in rubber mixtures.

Description

Oligomeric organosilanes, method for the production thereof and use thereof in rubber mixtures
Technical Field
The invention relates to oligomeric organosilanes, to a method for the production thereof and to the use thereof in rubber mixtures.
Background
It is known that sulfur-containing organosilicon compounds, such as 3-mercaptopropyltrimethoxysilane or bis (3- [ triethoxysilyl ] propyl) tetrasulfane, can be used as silane adhesion promoters or reinforcing assistants in rubber mixtures with oxidic fillers, for treads and other components of motor vehicle tires (DE 2141159, DE 2212239, US 3978103, US 4048206).
EP 0784072a1 discloses rubber mixtures based on at least one elastomer with silica and reinforcing assistants as filler, which are prepared by mixing at least one functional polyorganosiloxane compound or the in situ reaction product thereof, and which contain functional organosilanes as further constituents. The monomer units used are, in particular, 3-mercaptopropyltrialkoxysilanes or bis (trialkoxysilylpropyl) tetrasulfanes, each bearing 3 and 6 alkoxy substituents, respectively.
Furthermore, EP 0964021 discloses oligomeric organosilanepolysulfanes which do not condense to give solids and which contain structural units A and/or B and/or C in any linear, branched or cyclic arrangement. WO 2006/037380, EP 0997489 and EP 1273613 likewise disclose oligomeric organosilanes.
The known oligo/polysiloxanes have the disadvantage of poor processability and poor tear strength.
Disclosure of Invention
it is an object of the present invention to provide oligomeric organosilanes having improved processability and/or tear strength.
The present invention provides oligomeric organosilanes comprising at least two different structural units within the molecule, wherein the structural units are selected from structural units A, B, C and D, which are linked in any desired linear, branched or cyclic arrangement,
Wherein Y ═ H, F, Cl, Br, I, SCN, SH, -Sx-(CH2)nSiR1R2or-N (R)8)2；
R8Are identical or different and are H, (C)1-C16) Alkyl, preferably C4-alkyl, - (CH)2)2NH2、-(CH2)2NH-(CH2)2NH2Or- (CH)2)2N[(CH2)2NH2]2；
Wherein n-1-8, preferably n-2 or 3;
G＝H、F、Cl、Br、I、SCN、SH、-Sx-(CH2)nSiRR1R2or-N (R)8)2Wherein G is different from Y;
R、R1、R2、R3、R4、R7Each independently is OH; (C)1-C16) Alkyl, preferably methyl or ethyl; (C)2-C16) Alkenyl, preferably C2-an alkenyl group; (C)6-C14) An aryl group; (C)1-C4) Alkoxy, preferably methoxy or ethoxy; OSiR1R2R3Radical or alkyl polyether radical-O- (R)5-O)m-R6Wherein R is5Identical or different and branched or unbranched, saturated or unsaturated, aliphatic divalent C1-C30Hydrocarbyl, preferably- (CH)2)2-、-(CH2)3-or (CH)2C(CH3) H) -; m is on average 1 to 30, preferably 3 to 8, more preferably 5; and R6Is unsubstituted or substituted, branched or unbranched C1-C30Alkyl, preferably C11-C19an alkyl group; c2-C30Alkenyl, preferably C2An alkenyl group; c6-C14Aryl or C7-C40Aralkyl group;
x is statistically averaged from 1 to 6, preferably from 2 to 4;
z is on a statistical average 1 to 6, preferably 2 to 4;
Characterised by at least one R, R1、R2、R3、R4Or R7The radical is an alkyl polyether radical-O- (R)5-O)m-R6。
The alkyl polyether group may preferably be-O- (CH)2CH2-O)m-R6More preferably-O- (CH)2CH2-O)5-R6Most preferably-O- (CH)2CH2-O)5-C13H27。
The relative molar mass of the oligomeric organosilanes according to the invention, as measured by GPC, may be 400-100000g/mol, preferably 450-50000g/mol, more preferably 600-10000g/mol, compared with a standard consisting of a mixture of siloxanes of vinyltrimethoxysilane.
The oligomeric organosilanes may contain structural units A and B and C, where R7Is an alkyl polyether radical-O- (R)5-O)m-R6preferably R5＝-CH2CH2-, m is 5, and R6＝-C13H27. In this context, it is also possible for n to be 3 and Y to be SH; in the structural unit B, R1Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6，R2Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6n is 3, z is 2-4; and in the structural unit C, R ═ phenyl, propyl or octyl, and R3Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6. The molar ratio of the molar fraction of structural unit a to the sum of the molar fractions of structural units B and C may be greater than 1.
The oligomeric organosilanes may contain structural units A and B, where R7is an alkyl polyether radical-O- (R)5-O)m-R6Preferably R5＝-CH2CH2-, m is 5, and R6＝-C13H27. In this context, it is also possible for n to be 3 and Y to be SH in structural unit a and R to be in structural unit B1Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6，R2Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6N is 3 and z is 2-4. The molar ratio of the mole fraction of structural unit a to the mole fraction of structural unit B may be greater than 1.
The oligomeric organosilanes may contain structural units A and C, where R7Is an alkyl polyether radical-O- (R)5-O)m-R6preferably R5＝-CH2CH2-, m is 5, and R6＝-C13H27. In this context, it is also possible for n to be 3 and Y to be SH in the structural unit a and for R to be phenyl, propyl or octyl and R to be phenyl, propyl or octyl in the structural unit C3Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6. The molar ratio of the mole fraction of structural unit a to the mole fraction of structural unit C may be greater than 1.
The oligomeric organosilanes may contain structural units A and C and D, where R7Is an alkyl polyether radical-O- (R)5-O)m-R6Preferably R5＝-CH2CH2-, m is 5, and R6＝-C13H27. In this context, it is also possible for n to be 3 and Y to be SH in the structural unit a and for R to be phenyl, propyl or octyl in the structural unit C and for R to be3ethoxy or alkylpolyether radical-O- (R)5-O)m-R6And in the structural unit D, G ═ Cl or NH2，n＝3，R4Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6. The molar ratio of the molar fraction of structural unit a to the sum of the molar fractions of structural units C and D may be greater than 1.
The oligomeric organosilanes may contain structural units A and D, where R7Is an alkyl polyether radical-O- (R)5-O)m-R6Preferably R5＝-CH2CH2-, m is 5, and R6＝-C13H27. In this context, it is also possible for n to be 3 and Y to be SH in the structural unit a and for G to be Cl or NH in the structural unit D2，n＝3，R4Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6. The molar ratio of the mole fraction of structural unit a to the mole fraction of structural unit D may be greater than 1.
The oligomeric organosilanes of the invention may be cyclic, branched or linear via Y.
The compounds of the invention may be in the form of a single compound having a defined molecular weight or in the form of a mixture of oligomers having a molecular weight distribution.
Alkyl polyether radical-O- (R) in oligomeric organosilanes5-O)m-R6the molar ratio to silicon may be>0 and 2.0 or less, preferably>0.1 and less than or equal to 1.0. Alkyl polyether radical-O- (R)5-O)m-R6The molar ratio to silicon can be determined by the alkyl polyether group-O- (R)5-O)m-R6Is determined from the mole fraction of silicon. Alkyl polyether radical-O- (R)5-O)m-R6can be determined by the use of internal standards and known to those skilled in the art13CNMR spectroscopy. The internal standard substance canAs dimethyl terephthalate, naphthalene or other internal standards known to those skilled in the art for NMR spectroscopy. The mole fraction of silicon can be determined by means of methods known to those skilled in the art for determining the Si content (e.g. ASTM 6740).
The invention also provides a process for preparing the oligomeric organosilanes according to the invention, characterized in that,
In a first step, the compounds of the formulae I to IV are oligomerized/polymerized according to molar ratios in the presence of water at temperatures of from 0 to 150 ℃, preferably from 20 to 130 ℃, more preferably from 80 to 120 ℃, where Y, G, R, R1、R2、R3、R4、R5、R6、R7、R8N, m, u, x and z are each as defined above, and R9Is H, F, Cl, Br, I, (C)1-C16) An alkoxy group, preferably a methoxy or ethoxy group,
And in a second step with the formula HO- (R)5-O)m-R6The alkyl polyether alcohol of (1).
according to the process of the present invention, the first step and the second step may be carried out in the presence of a catalyst. Wherein the catalysts in the first and second steps may be the same or different. The catalyst may be added in catalytic or stoichiometric amounts herein. Of these, various acidic, basic or nucleophilic catalysts known to the person skilled in the art from the SOLGEL chemistry of akoxysilanes (cf. for example R.Corriu, D.Leclercq, Angew.Chem.1996, 108, 1524-. It is not important whether the catalyst is in phase with the reaction solution (homogeneous catalysis) or in solid form (heterogeneous catalysis), and the catalyst is removed after the reaction is complete.
Preference is given to carrying out the homogeneous catalysis using Lewis acids such as tetrabutyl orthotitanate, or by nucleophilic methods using ammonium fluoride, or by heterogeneous catalysis using aluminum oxide. Base catalysis can be carried out using, for example, organic bases such as triethylamine, tetramethylbenzenePiperidine, tributylamine or pyridine, or using inorganic bases such as NaOH, KOH, Ca (OH)2、Na2CO3、K2CO3、CaCO3、CaO、NaHCO3、KHCO3Or alkoxides such as NaOCH3or NaOC2H5To proceed with. Nucleophilic catalysis can be accomplished using any desired fluoride, such as ammonium fluoride, sodium fluoride, potassium fluoride, or any desired tetraalkylammonium fluoride, such as tetrabutylammonium fluoride. Acid catalysis can be carried out using dilute aqueous mineral acids or solutions of lewis acids in water. The catalysis can preferably be carried out using dilute aqueous HCl or sulfuric acid, with 0.1 mol% of catalyst being used, based on the amount of silane used.
Very preferably the catalyst used may be tetrabutyl orthotitanate, KOH, NaOH, ammonium fluoride or HCl.
It is particularly preferred to use HCl as catalyst in the first step and tetrabutyl orthotitanate as catalyst in the second step.
the process according to the invention can be carried out in the presence of a solvent.
The oligomerization/polymerization reaction is carried out with the addition of water, with elimination of alcohol, hydrogen halide or hydrogen, and can be carried out here or in an inert organic solvent or mixtures thereof, for example in an aromatic solvent such as chlorobenzene, a halogenated hydrocarbon such as chloroform, dichloromethane, an ether such as diisopropyl ether, methyl tert-butyl ether, tetrahydrofuran or diethyl ether, acetonitrile or a carboxylic acid ester such as ethyl acetate, methyl acetate or isopropyl acetate, an alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol or tert-butanol. Preferred solvents herein are ethanol or ethyl acetate.
The second step can be carried out without further addition of solvent.
The compound of formula I may be, for example:
3-mercaptopropyltrimethoxysilane, a compound of formula (I),
3-mercaptopropyltriethoxysilane (PTS),
Bis (3- [ triethoxysilyl ] propyl) disulfane,
bis (3- [ triethoxysilyl ] propyl) trisulfane,
Bis (3- [ triethoxysilyl ] propyl) tetrasulfane,
3-thiocyanatopropyltrimethoxysilane,
3-thiocyanatopropyltriethoxysilane,
3-amino propyl trimethoxy silane and the amino propyl trimethoxy silane,
3-amino propyl triethoxy silane is added,
Or
The compound of formula II may be, for example:
Bis (3- [ triethoxysilyl ] propyl) disulfane,
Bis (3- [ triethoxysilyl ] propyl) trisulfane, or
Bis (3- [ triethoxysilyl ] propyl) tetrasulfane.
The compound of formula III may be, for example:
The methyl trimethoxy silane is used as the main component,
The methyl-triethoxysilane compound is used as a raw material,
A phenyl-trimethoxy silane,
the content of the phenyl-triethoxysilane is as follows,
The propyl trimethoxy silane is used for preparing the acrylic resin,
The propyl-triethoxy silane is added into the raw materials,
Octyl-trimethoxy-silane is added to the reaction mixture,
the content of the octyl-triethoxy silane is as follows,
Hexadecyl trimethoxy silane is added into the reaction kettle,
The hexadecyl triethoxy silane is added into the reaction kettle,
the reaction product of dimethyl dimethoxy silane and dimethyl dimethoxy silane,
Dimethyldiethoxysilane, or
Dichlorodimethylsilane.
the compound of formula IV may be, for example
3-mercaptopropyltrimethoxysilane, a compound of formula (I),
3-mercaptopropyltriethoxysilane (PTS),
bis (3- [ triethoxysilyl ] propyl) disulfane,
Bis (3- [ triethoxysilyl ] propyl) trisulfane,
Bis (3- [ triethoxysilyl ] propyl) tetrasulfane,
3-thiocyanatopropyltrimethoxysilane,
3-thiocyanatopropyltriethoxysilane,
3-chloropropyl-trimethoxyl silane is used as the raw material,
3-chloropropyl-triethoxysilane (HCP),
3-amino propyl trimethoxy silane and the amino propyl trimethoxy silane,
3-amino propyl triethoxy silane is added,
Or
When the reaction is complete, the volatile constituents can be removed according to ways known to those skilled in the art, distillation being preferred. The catalyst may be deactivated, preferably by neutralization, or preferably removed by filtration.
The invention also provides for the use of the organosilanes of the invention in rubber mixtures.
The invention also provides rubber mixtures comprising the oligomeric organosilanes of the invention. The rubber mixtures according to the invention can be used for producing shaped bodies, in particular pneumatic tires or tire treads.
The rubber mixtures of the invention may comprise rubber, filler, preferably precipitated silica, optionally in the presence of further rubber auxiliaries, and at least one oligomeric organosilane. The oligomeric organosilanes may be used in amounts of from 0.1 to 15% by weight, based on the amount of rubber used.
The use of the oligomeric organosilanes according to the invention in the rubber mixing process significantly reduces the unpleasant alcoholic odor released as a result of the precondensation which has already taken place. The generation of alcohol during the mixing operation is reduced compared to the conventional operation mode, for example, by simply using bis (3- [ triethoxysilyl ] propyl) tetrasulfane (TESPT) as an adhesion promoter.
The addition of the oligomeric organosilanes according to the invention and of the filler is preferably carried out at a mass temperature of 100 ℃ and 200 ℃ but can also be carried out later at a lower temperature (40 ℃ to 100 ℃), for example together with other rubber auxiliaries.
the oligomeric organosilanes may be added in pure form to the mixing operation or applied to an inert organic or inorganic support. Preferred support materials are silica, natural or synthetic silicates, alumina or carbon black.
the fillers used in the rubber mixtures according to the invention may be:
-carbon black: the carbon blacks used here are prepared by the lamp black process, furnace black process or gas black process and have BET surface areas of from 20 to 200m2And/g, for example SAF black, ISAF black, HSAF black, HAF black, FEF black or GPF black. The carbon black may also optionally contain heteroatoms, such as Si.
silicas, preferably precipitated silicas, prepared, for example, by precipitation of silicate solutions or flame hydrolysis of silicon halides, with specific surface areas of 5 to 1000, preferably 20 to 400m2in terms of the BET surface area, and the primary particle size is from 10 to 400 nm. The silica may also optionally be in the form of mixed oxides with other metal oxides, such as aluminum oxide, magnesium oxide, calcium oxide, barium oxide, zinc oxide and titanium oxide.
Synthetic silicates, e.g. aluminum silicate, alkaline earth metal silicates, e.g. magnesium silicate or calcium silicate, having BET surface areas of 20 to 400m2In terms of a/g and a primary particle diameter of 10 to 400 nm.
Natural silicates, such as kaolin and other naturally occurring silicas.
Glass fibers and glass fiber products (mats, strands) and glass microbeads.
Preference is given to using from 5 to 150 parts by weight of a BET surface area of from 20 to 400m, based in each case on 100 parts of rubber2Per g of carbon black, or 5 to 150 parts by weight of a BET surface area of 20 to 400m, obtained by precipitation of a silicate solution2Per g of finely divided silica.
The fillers mentioned may be used individually or in the form of mixtures. In carrying out a particularly preferred process, from 10 to 150 parts by weight of light-coloured filler, optionally together with from 0 to 100 parts by weight of carbon black, and from 0.3 to 10 parts by weight of the oligomeric organosilanes according to the invention, based in each case on 100 parts by weight of rubber, can be used for preparing the mixtures.
For the preparation of the rubber mixtures according to the invention, not only natural rubber but also synthetic rubber are suitable. Preferred synthetic rubbers are described, for example, in W.Hofmann, Kautschuktechnology [ Rubber Technology ], Genter Verlag, Stuttgart 1980. They include:
Polybutadiene (BR)
Polyisoprene (IR)
Styrene/butadiene copolymers (SBR) having a styrene content of from 1 to 60% by weight, preferably from 2 to 50% by weight
isobutylene/isoprene copolymer (IIR)
Butadiene/acrylonitrile copolymers (NBR) having an acrylonitrile content of 5 to 60% by weight, preferably 10 to 50% by weight
Partially hydrogenated or fully hydrogenated NBR rubber (HNBR)
ethylene/propylene/diene copolymers (EPDM)
And mixtures of these rubbers. For the preparation of motor vehicle tires, anionically polymerized L-SBR rubbers with glass transition temperatures above-50 ℃ are preferred, in particular their mixtures with diene rubbers.
the rubber vulcanizates of this invention may contain other rubber auxiliary products such as reaction accelerators, aging stabilizers, heat stabilizers, light stabilizers, antiozonants, processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, flame retardants, metal oxides, and activators such as triethanolamine, polyethylene glycol, hexanetriol, which are well known in the rubber industry.
The use of rubber aids is guided by the usual amounts due to factors including end use. Typical amounts are, for example, from 0.1 to 50% by weight, based on the amount of rubber. The oligomeric organosilane may act alone as a crosslinker. In general, it may be advisable to add further crosslinkers. Other known cross-linking agents that may be used are sulfur or peroxides. The rubber mixtures according to the invention may additionally comprise vulcanization accelerators. Examples of suitable vulcanization accelerators are mercaptobenzothiazoles, sulfonamides, guanidines, thiurams, dithiocarbamates, thioureas and thiocarbonates. The vulcanization accelerator and sulfur or peroxide may be used in an amount of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on the amount of rubber.
The vulcanization of the rubber mixtures according to the invention can be carried out at temperatures of 100 ℃ and 200 ℃, preferably at temperatures of 130 ℃ and 180 ℃, optionally at pressures of 10 to 200 bar. The mixing of the rubber with the filler, any rubber auxiliaries and the oligomeric organosilanes according to the invention can be carried out in conventional mixing units, for example roll mills, internal mixers and mixing extruders. The rubber vulcanizate of the present invention is suitable for use in the production of molded articles. The rubber mixtures according to the invention can be used for producing tires, profiles (profiles), cable sheathing, hoses, drive belts, conveyor belts, tire casings, shoe soles, sealing rings and damping elements.
The present invention also provides oligomeric organosilanes obtainable according to the process of the invention.
The oligomeric organosilanes according to the invention have the advantage, in rubber mixtures, of improved processability and/or improved tear strength.
SH- (mercapto), S2- (disulfane), S3- (trithiolane), Sx- (where x>3 polysulfanes) can be used1H NMR spectroscopy.
The molar fractions of SiOEt and SiOR groups can be determined by those skilled in the art13C NMR spectroscopy.
Furthermore, the monomer content, as well as the M structure, D structure and T structure, can be used, as is likewise well known to the person skilled in the art29Si NMR spectroscopy.
the molar mass and the molar mass distribution can be determined by Gel Permeation Chromatography (GPC). GPC analysis methods are described in detail in, including "Modern Size-Exclusion Liquid Chromatography", Andre Striegel et al, Wiley&Sons, second edition, 2009. It comprises a mixture of siloxanes (vinyltrimethoxysilane, divinyltetramethoxydisiloxane, trivinylhexamethoxytrisiloxane, tetravinyloctamethoxytetrasiloxane) using vinyltrimethoxysilane as a standard for calibrating the siloxane analysis method. The columns used were: (MZ-Analysetechnik): column: 50X 8.0mm, MZ-Gel SDplus (styrene/divinylbenzene copolymer with high crosslinking level, spherical particle type), porosity 50A (angstroms,) 5 μm (micron) (front column), 300X 8.0mm, MZ-Gel SDplus, porosity 100A (angstroms,) 5 μm (micrometers), 300X 8.0mm, MZ-Gel SDplus, porosity 500A (angstroms,) 5 μm; eluent and pump flow rates: methyl Ethyl Ketone (MEK), 1ml/min, standard: internal standard-1 g/l of ethylbenzene in a 1% sample solution. The instrument is calibrated beforehand with respect to suitable substances (monomers, dimers, trisiloxanes, etc.). Instrument (Agilent): 1100 series isocratic pump G1310A, 1100 series column incubator G1316A, 1100 series RID detector G1362A, manual sample injector G1328A, vacuum degassingG1322A, GPC software (PSS WinGPC Unity).
Examples
Octyl triethoxysilane, propyl triethoxysilane,9265 (Phenyltriethoxysilane), Si(bis (triethoxysilylpropyl) tetrasulfide) and VP Si(3-mercaptopropyltriethoxysilane) is a silane from Evonik Industries.
Marlosol is of the formula HO- (R) from Sasol5-O)m-R6In which R is5＝CH2CH2，R6＝C13H27And m is 5.
Example 1
From VP SiPreparation of/octyl triethoxysilane/Marlosol (1:0.5:0.5) — 0.8 equivalent of water
First, VP Si is added(417g) And octyl triethoxysilane (242g) were added to the stirring apparatus and heated to 85 ℃. A mixture of water (38g) and concentrated HCl (0.3g, 37%) in ethanol (363g) was then added dropwise and the mixture was stirred for 8.5 hours. After the oligomerization reaction was completed, the solvent and alcohol formed in the hydrolysis were removed under reduced pressure. Marlosol (368g) and tetra-n-butyl titanate (0.5g) were added and heated to 140 ℃ for 1 hour. The ethanol formed was removed by distillation under reduced pressure. The bottom product (733g, 95% of theory) was a viscous orange liquid.
Density (20 ℃): 1.012g/cm3
29Si NMR：3% silane (VP Si)Octyl triethoxysilane), 49% M structure, 40% D structure, 9% T structure
GPC：Mn＝967g/mol，Mw＝1234，Mz＝1536，PDI＝1.2761
Alkyl polyether radical-O- (R)5-O)m-R6Molar ratio to silicon is 0.33
Example 2
From VP SiPreparation of/propyltriethoxysilane/Marlosol (1:0.5:0.5) — 0.8 equivalent of water
First, VP Si is added(417g) And propyltriethoxysilane (181g) were added to the stirring apparatus and heated to 85 ℃. A mixture of water (38g) and concentrated HCl (0.3g, 37%) in ethanol (363g) was then added dropwise and stirred for 8 hours. After the oligomerization reaction was completed, the solvent and alcohol formed in the hydrolysis were removed under reduced pressure. Marlosol (368g) and tetra-n-butyl titanate (0.5g) were added and heated to 140 ℃ for 1 hour. The ethanol formed was removed by distillation under reduced pressure. The bottom product (751g, 94% of theory) was a viscous colorless liquid.
Density (20 ℃): 1.029g/cm3
13C NMR：78.6mol％SiOEt，21.4mol％SiOR
29Si NMR：<1% silane (VP Si)propyltriethoxysilane), 60% M structure, 35% D structure, 4% T structure
GPC：Mn＝757g/mol，Mw＝1066，Mz＝1417，PDI＝1.4082
Alkyl polyether radical-O- (R)5-O)m-R6Molar ratio to silicon is 0.33
example 3
From VP SiPhenyltriethoxysilane (A)9265) Marlosol (1:0.5:0.5) — 0.8 equivalent of water
first, VP Si is added(417g) and9265(210g) was added to the stirring device and heated to 88 ℃. A mixture of water (38g) and concentrated HCl (0.3g, 37%) in ethanol (363g) was then added dropwise and the mixture was stirred for 6 hours. After the oligomerization reaction was completed, the solvent and alcohol formed in the hydrolysis were removed under reduced pressure. Marlosol (368g) and tetra-n-butyl titanate (0.5g) were added and heated to 140 ℃ for 1 hour. The ethanol formed was removed by distillation under reduced pressure. The bottom product (797g, 99% of theory) was a viscous, light yellow liquid.
density (20 ℃): 1.050g/cm3
29Si NMR：3％VP Si1％9265, 51% M structure, 37% D structure, 8% T structure
GPC：Mn＝770g/mol，Mw＝1013，Mz＝1300，PDI＝1.3156
alkyl polyether radical-O- (R)5-O)m-R6Molar ratio to silicon is 0.33
Example 4
The invention comprises the following steps: from VP Si/SiMarlosol (1:0.5:0.5) — 0.8 equivalent of water
First, VP Si is added(417g) And Si(466g) Added to a stirring device and heated to 98 ℃. A mixture of water (38g) and concentrated HCl (0.3g, 37%) in ethanol (363g) was then added dropwise and the mixture was stirred for 8 hours. After the oligomerization reaction was completed, the solvent and alcohol formed in the hydrolysis were removed under reduced pressure. Marlosol (368g) and tetra-n-butyl titanate (0.5g) were added and heated to 140 ℃ for 1 hour. The ethanol formed was removed by distillation under reduced pressure. The bottom product (1028g, 98% of theory) was a viscous, yellow liquid.
Density (20 ℃): 1.082g/cm3
1H NMR：40mol％SH，22mol％S2，27mol％S3，11mol％Sx
13C NMR：87.5mol％SiOEt，22.5mol％SiOR
29Si NMR: 9% silane, 72% M structure, 19% D structure
GPC：Mn＝1317g/mol，Mw＝5501，Mz＝12291，PDI＝4.1778
Alkyl polyether radical-O- (R)5-O)m-R6molar ratio to silicon is 0.33
Comparative example 5
Reference is made to EP 0964021: from SiPreparation of/PTEO (1:5) -0.8 equivalent of Water
Firstly, Si is firstly added(240g) And PTEO (464g) was added to the stirring device and heated to 75 ℃. Then dropwise adding into ethanol(436g) A mixture of water (45g) and concentrated HCl (0.5g, 37%) and the mixture was stirred for 12 hours. After the oligomerization reaction was completed, the solvent and alcohol formed in the hydrolysis were removed under reduced pressure. The bottom product (518g,>99% of theory) is a viscous yellow liquid.
29Si NMR: 0% silane PTEO, 0.4% silane Si1% M-structured PTEO, 69% M-structured Si 69+ D-structured PTEO, 28% D-structured Si+ T structure PTEO, 1% T structure Si
GPC：Mn＝871g/mol，Mw＝1473，Mz＝2337，PDI＝1.6916
Example 6
Table 1 below shows the formulations used for the rubber mixtures. Wherein the unit phr means parts by weight based on 100 parts by weight of the raw rubber used. Based on the silane used in the in situ reaction, equimolar amounts of oligomeric silane are used. The mixture was prepared in a 1.5 liter mixer (type E) at a batch temperature of 155 ℃.
TABLE 1
Polymer VSL 5025-2 was a solution polymerized SBR copolymer from Bayer AG having a styrene content of 25 wt% and an ethylene base of 50 wt%. The copolymer contained 37.5phr of TDAE oil and had a Mooney viscosity (ML 1+4/100 ℃ C.) of 47.
The polymer Buna CB 24 is cis-1, 4-polybutadiene (neodymium type) from Bayer AG with a cis-1, 4 content of at least 96% and a Mooney viscosity of 44. + -.5.
Ultrasil 7000GR is an easily dispersible silica from Evonik Industries AG and BET surface areaIs 170m2/g。
The TDAE oil used was Vivatec 500 from Klaus Dahleke KG, Vulkanox 4020 was 6PPD from Lanxess Europe GmbH & co.kg, Vulkanox HS/LG was TMQ from Lanxess, and Protektor G3108 was an antiozonant wax from Paramelt b.v.; ZnO RS is ZnO from Arnsperger Chemikalien GmbH; EDENOR ST1 GS 2.0 is palmitic/stearic acid from Caldic Deutschl and GmbH & co.kg; aktiplast ST is a plasticizer from rhein chemie, consisting of a mixture of hydrocarbons, zinc soaps and fillers. Rhenogran DPG-80 comprises 80% DPG on EVA/EPDM support from RheinChemie and Vulkacit CZ is CBS from Lanxess Europe GmbH & Co. Perkacit TBzTD (tetrabenzylthiuramed disulfide) is a product from Flexsys n.v.
The rubber mixtures were prepared in an internal mixer according to the three stages of table 2.
Table 2:
a general process for preparing Rubber mixtures and vulcanizates thereof is described in "Rubber Technology Handbook", W.Hofmann, Hanser Verlag 1994.
the rubber tests were carried out by the test methods given in table 3.
Table 3:
Vulcanization was carried out at 165 ℃ for 15 minutes. Table 4 shows rubber data for the raw materials and the vulcanized products.
TABLE 4
Compared with equimolar in situ-formed mixtures or oligomeric organosilanes according to EP 0964021, rubber mixtures containing the oligomeric silanes according to the invention exhibit improved processing properties (reduced torque after the 3 rd mixing stage), improved reinforcing properties (increased modulus and higher reinforcement index), improved rolling resistance and improved tear strength.

Claims (17)

1. An oligomeric organosilane containing at least two different structural units in the molecule, wherein said structural units are selected from structural units A, B, C and D connected in any desired linear, branched, or cyclic arrangement,
Wherein Y is SH or-Sx-(CH2)nSiRR1R2，
n＝1-8，
G ═ SH or-Sx-(CH2)nSiRR1R2Wherein G is different from Y,
R、R1、R2、R3、R4Each independently is OH, (C)1-C16) Alkyl, (C)2-C16) Alkenyl, (C)6-C14) Aryl group, (C)1-C4) Alkoxy, OSiR1R2R3Radical or alkyl polyether radical-O- (R)5-O)m-R6Wherein R is5Identical or different and branched or unbranched, saturated or unsaturated, aliphatic divalent C1-C30A hydrocarbyl group, m is on average 1 to 30, and R6Is unsubstituted or substituted, branched or unbranched C1-C30Alkyl radical, C2-C30Alkenyl radical, C6-C14aryl or C7-C40An aralkyl group,
x is statistically averaged to be 1 to 6,
The statistical average of z is 1-6,
It is characterized in thatin, R7The radical is an alkyl polyether radical-O- (R)5-O)m-R6And the oligomeric organosilane comprises structural units A, B and C; structural units A and B; structural units A and D; structural elements A, C and D; or structural units a and C.
2. The oligomeric organosilane according to claim 1, characterized in that it has a molecular weight of 400-100000 g/mol.
3. An oligomeric organosilane according to claim 1, characterized in that it comprises structural units a and B and C, and in said structural units a n-3, Y-SH; in the structural unit B, R1Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6，R2Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6N is 3, z is 2-4; and in the structural unit C, R ═ phenyl, propyl or octyl, and R3Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6。
4. the oligomeric organosilane of claim 3, wherein the molar ratio of the mole fraction of structural unit A to the sum of the mole fractions of structural units B and C is greater than 1.
5. An oligomeric organosilane according to claim 1, characterized in that it comprises structural units a and B and in said structural units a n-3, Y-SH; in the structural unit B, R1ethoxy or alkylpolyether radical-O- (R)5-O)m-R6，R2Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6，n＝3，z＝2-4。
6. The oligomeric organosilane of claim 5, wherein the molar ratio of the mole fraction of said structural unit A to the mole fraction of said structural unit B is greater than 1.
7. An oligomeric organosilane according to claim 1, characterized in that it comprises structural units a and C and in said structural units a n-3, Y-SH; and in the structural unit C, R ═ phenyl, propyl or octyl, and R3Ethoxy or alkylpolyether radical-O- (R)5-O)m-R6。
8. The oligomeric organosilane of claim 7, wherein the molar ratio of the mole fraction of structural unit A to the mole fraction of structural unit C is greater than 1.
9. A process for preparing an oligomeric organosilane according to any of claims 1 to 8,
In a first step, the compounds of the formulae I to IV are oligomerized/polymerized in the presence of water at a temperature of from 0 to 150 ℃ in terms of molar ratio,
And in a second step with an alkyl polyether alcohol HO- (R)5-O)m-R6reaction of Y, G, R, R1、R2、R3、R4、R5、R6、R7N, m, x and z are each as defined in claim 1, and R9is H, F, Cl, Br, I, (C)1-C16) An alkoxy group.
10. A process for preparing an oligomeric organosilane according to claim 9, characterized in that the reaction is carried out in the presence of a catalyst.
11. A process for preparing an oligomeric organosilane according to claim 10, characterized in that the catalyst in the first step is HCl and the catalyst in the second step is tetrabutyl orthotitanate.
12. A process for preparing an oligomeric organosilane according to any of claims 9 to 11, characterized in that the reaction is carried out in a solvent.
13. A process for preparing an oligomeric organosilane according to claim 12, characterized in that the solvent is ethyl acetate or ethanol.
14. use of an oligomeric organosilane according to any of claims 1 to 8 in rubber mixtures.
15. A rubber compound comprising the oligomeric organosilane of any of claims 1-8.
16. A rubber mixture as claimed in claim 15, characterized in that 0.1 to 15% by weight, based on the amount of rubber used, of the oligomeric organosilane is used.
17. Use of the rubber mixtures according to claim 15 or 16 for the preparation of tires, profiles, cable sheathing, hoses, drive belts, conveyor belts, tire casings, shoe soles, sealing rings and damping elements.
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